Quaternary ammonium compound and process of making the same



' is liquid, an excess thereof may be employed as Patented Nov. 24, 1942UNITED STATES PATENT FIcE cummin AMMONIUM COMPOUND AND aggnocnss orMAKING THE SAME 7 y i Alfred William Baldwin and Henry Alfred Piggott,Blackley, Manchester, England, assignors to Imperial Chemical Industriesporation of Great Britain Limited, a cor- No'Dr'awing. ApplicationAugust 23, 1938, Serial l$6226,376. In Great Britain February'27,

This

application is a continuation-in-part of our copending applicationSerial No. 126,478,

filed February 18, 1937 (now Patent No. 2,131,362,

issued September 27,1938).

In said copending application we have disclosed and claimed certainhalogen compounds of the general-formulae R-CO-N-CHr-Hal andRQ-CO-N-CIIr-Hal wherein R and R each stand for an aliphatic orcycloaliphatic hydrocarbon radical, while Hal standsfor halogen. We havefurther disclosed in said copendin application that by reaction withtertiary bases, for example pyridine or quinoline, the halides abovereferred to yield novel quaternary ammonium compounds of the generalformulae RCO-N-OHzN(tert)Hal and RO-CO-N-OHaN(tert)Hal wherein R and Bhave the same significance as above while N (tert) is the radical of atertiary base.

the aforesaid quaternary ammonium compounds. It is accordingly .anobject of this invention to provide novel quaternary compounds of theabove general formula, and processes for preparing the same. Other andfurther objects of this invention will appear as the descriptionproceeds.

instance diethyl ether, acetone, methyl-ethylketone or ethylenedichloride. The solvent is not essential, it serves as a diluent todiminish the vigour of the reaction. Where the base employed Our presentapplication deals particularly with pound N-cyclohexyllauramidomethylreclaims. (01. 260-295) solvent. The quaternary ammonium compound,

being insoluble in such solvents in the cold," precipitates out and maybe filtered off.

The novel quaternary compoundsare generally solids at ordinarytemperatures soluble in water,

alcohol, warm benzene and ethylene dichloride.

But their most valuable characteristic, from a technical viewpoint, isthe fact that whenapplied to textile fiber, for instance naturalor-artificial cellulose, according to copending application of Baldwinet a1. Serial No.- 113,702 (now Patent No. 2,278,417, issued April 7,1942) they impart to the'fiber a water-repellent finish of a permanentcharacter, that is one withstanding treatment with soap and alkalies.

Without limiting our inventionto any particular procedure the followingexamples in which parts by weight are given will serve to illustrateourpreferred mode of operation.

Example 1. 10 parts of laurocyclohexylamide. (M. P. to 76 0., obtainedby interaction or lauric acid chloride and cyclohexyl-amlne) are mixedwith 4.4 parts of para-formaldehyde and parts of dry benzene in a vesselfitted with a suitable condenser arranged for distillation. Thetemperature is raised until the reaction mixture boils gently, and dryhydrogen chloride gas is passed in.

Wateris formed in the reaction which takes place, and is allowed todistill over slowly as an azeotropic mixture with benzene. The passingof hydrogen chloride and the slow distillation is proceeded with untilno'more water passes'over, that is, until the distillatecomes overclear. The residual benzene is evaporated from the reaction mixtureunder diminished pressure, the cooled residue is extracted. with colddry ether and filtered. By evaporating the ethereal filtrate there isobtained a new chlorine-containing comchloride corresponding to theformula curiae 0-N-cn,o1

if pyridine is added to the ethereal filtrate obtained as above, thereis precipitateda quaternary pyridinium salt which maybe filtered oil.This quaternary salt is soluble in cold water to give foaming solutionswhich solutions los their foaming power when boiled.

Example 2.--25 parts'of stearomethylamide, which" may be made byinteracting stearic acid or stearyl chloride with methylamine, and 2.6parts of para-formaldehyde are suspended in 150 parts of dry benzene.Gaseous hydrogen chloride is passed into the stirred mixture, keepingthe temperature below 10 C. until the saturation point is reached andno'solid remains undissolved in the benzene. 20 parts of freshlydehydrated magnesium sulphate are then added to absorb the water whichwill be produced when the temperature of the benzene solution is slowlyraised to boil. After heating at the boil for 5 to minutes the reactionmixture is filtered and the benzene evaporated from the filtrate. Theresidue so obtained is extracted with petroleum ether (B. P. 40 to 60C.),'the ether extract after standing at to C. for a short time isfiltered, and the product is recovered from the filtrate by evaporatingthe petroleum ether, pref erably under reduced pressure. The product soobtained is a low-melting, waxy sold containing combined chlorine whichfumes somewhat inmoist air. The new compound is believed to beN-methyl-stearamidomethyl chloride, and to have the formula cmmco-n-omcx34.5 parts of this chloride are mixed with 200 parts of pyridine, andthe reaction product which separates out is filtered off. It may bewashed with acetone to free it from excess pyridine. The white productis soluble in water and alcohol. When cellulosic material is treatedwith a dilute solution of this product and heated in an oven with rapidair circulation to from 120 to 170 C. it becomes strongly waterrepellent. Repeated washings do notdiminish this property.

Example 3.34.5 parts of the N-methyl-stearamido-methyl-chloride obtainedin Example 2 are gradually stirred into 200 parts of acetone containing6 parts of trimethyl amine. The white solid which separates out isfiltered off and dried. It dissolves readily in water at C., and also inalcohol, benzene and ethylenedichloride.

Example 4.30 parts of methyl heptadecylcarbamate (American ChemicalJournal 1899, 22, 14) and 3 parts of para-formaldehyde are suspended in100 parts of dry benzene. Gaseous hydrogen chloride is passed into thestirred mixture, keeping the temperature below 10 C. until a clearbenzene solution saturated with hydrogen chloride is obtained. Water isproduced in the reaction which takes place and the reaction mixtureseparates into two layers. The lower aqueous layer is removed and theupper benzene layer is dried by standing over calcium chloride. Thedried benzene solution is filtered, and the product is recovered fromthe filtrate by evaporating the benzene, preferably under reducedpressure. The product is a colorless oil containing combined chlorine.It tends to crystallize on standing at atmospheric temperature and fumesin moist air. The new compound is believed to beN-carbomethoxyheptadecylamino-methyl chloride and to have the formula 36parts of this chloride are thoroughly mixed with 12 parts of pyridine.The two products react readily with liberation of heat. The resultingproduct may be freed from the excess of pyridine by washing with asolvent like ether or acetone. It is water soluble and has considerablefoaming properties.

Example 5.-25 parts of methyl undecylcarbamate (American ChemicalJournal, 1899, .22, 14) and 5 parts of para-formaldehyde are suspendedin 120 parts of dry benzene. Gaseous hydrogen chloride is passed intothe stirred mixture, keeping the temperature below 10 C., until a clearbenzene solution saturated with hydrogen chloride is obtained. Water isproduced in the reaction and the reaction mixture separates into twolayers. The lower aqueous layer is removed, and the upper benzene layeris dried by standing over calcium chloride and the product is isolatedby evaporating the benzene, preferably under reduced pressure. Theproduct is a light colored oil, and can be distilled as a colorless oil,boiling point 98 C., under a pressure of 10 to 3 mm. of mercury. Itfumes in moist air, and is obtained in 66% yield of distilled material.The new compound is believed to be N-carbomethoxyundecylaminomethylchloride, and to have the formula omoooimomoi uHu 27.3 parts of thischloride are dissolved in 100 parts of diethyl-ether and gradually addedto 200 parts of ether which contain 8 parts of pyridine. A precipitateis formed which is soluble in cold water and alcohol.

Example 6.--20 parts of .methyl butylcarbamate (Receiul des travauxchimiques des Pays- Bas 1895, 14, 18) and 8 parts of para-formaldehydeare suspended in parts of dry benzene. Gaseous hydrogen chloride ispassed into the stirred mixture, keeping the temperature below 10 C.,until a clear benzene solution saturated with hydrogen chloride isobtained. Water is produced in the reaction, and the reaction mixtureseparates into two layers, the lower aqueous layer being then removedand the upper benzene layer dried over calcium chloride. The product isrecovered by evaporating the benzene from the dried benzene layer anddistilling the residue. The product boils at 28 C., under a pressure of10 to 3 mm. of mercury and is obtained in a 66% yield of distilledmaterial. The new compound is believed to beN-carbomethoxybutylaminomethyl chloride, and to have the formula 18parts of this product are mixed with 20 parts of dry pyridine. The solidreaction product may be freed from the excess of pyridine by extractionwith ether or acetone. It is readily soluble in water and alcohol.

Example 7.-12 parts of acetoundecylamide (which may be made by theinteraction of undecylamine and acetyl chloride (and 2 parts ofpara-formaldehyde are suspended in 60 parts of dry benzene. Gaseoushydrogen chloride is passed into the stirred mixture, keeping thetemperature below 10 C. until a. clear benzene solution saturated withhydrogen chloride is obtained. The benzene solution is dried overcalcium chloride and evaporated to dryness. The residue so obtained isextracted with petroleum ether, boiling point 40 to 60 C. and the etherextract after standing at 15 to 20 C. for a short time is filtered andthe product recovered from the filtrate by evaporating the petroleumether, preferably under reduced pressure. The new compound so obtainedis believed to be N-acetoundecylamidomethyl chloride and to have theformula CHaCO.N.CHrCi Cu zz 26.1 parts of this chloride were addedgradually to a solution of methyl-diethylol amine in acetone. Thequarternary ammonium compound which precipitates is water soluble andfoams strongly. v

Example 84-9 parts of stearomethylamide and 3 parts of parafcrmaldehydeare suspended in 200 parts of boiling benzene in a vessel fitted with asuitable condenser arranged for distillation.

Gaseous hydrogen chloride is passed in, and the water produced in thereaction allowed to distill of! as an azeotropic mixture with benzeneand so be removed from the reaction mixture. This procedure is continueduntil water no longer distills over with the benzene. The reactionmixture is then cooled, filtered and the filtrate is evaporated todryness.

The residue so-obtained 4 is extracted with petroleum ether (B. P. 40 to60 C.), the ether extract after standing at 15 to C. for a short time isfiltered and the product recovered from the filtrate by evaporating thepetroleum ether, preferably under reduced pressure. The productso-obtained is a lowmelting, waxy solid identical in behaviounwith theproduct of Example 2 and has a similar composition, that is, it isbelieved to be N-methylstearamidomethyl chloride.

34.5 parts of this chloride are mixed with 11.5

parts of commercial pyridine bases. The quar-.

ternary salt may be washed with acetone to remove the excess of thepyridine bases. It is soluble in warm water and decomposes when theaqueous solution is boiled or made alkaline with caustic alkalies.

Example 9.-If in Example 2 gaseous hydrogen bromide is used in place ofhydrogen chloride there is obtained a yellow crystalline solid whichcontains combined bromine and which reacts readily with tertiary amines,e. g. pyridine, in the cold. The new bromine containing compound isbelieved to be N-methylstearamidomethyl bromide, corresponding to theformula.

cnmlc 0.Nom.m

wherein Y'stands for a radical of the group consisting of alkyl, alkoxy,cycloalkyl and cycloalkoxy, N(tert) stands for the molecule of anitrogenous tertiary base, R stands for a member of stands for themolecule of a nitrogenous tertiary base, while x stands for halogen. I

3. A quaternary compound or the general 101". mula wherein Y stands foran aliphatic hydrocarbon radical having not less than 9 carbon atoms, Rstands for a member of the group consisting of aliphatic andcycloaliphatic hydrocarbon radlcals of not more than 7 carbon atoms,while X stands for halogen.

4. A quaternary ammonium compound of the general formula i cum-con-cm-N(tom-Cl wherein N(tert) stands for the molecule of a nitrogenoustertiary base. said compound being obtainable by reactingN-cyclohexyl-lauramidomethyl-chloride with a tertiary nitrogenous base,.and being a solid, soluble in water, alcohol, warm benzene andethylenedichloride.

5. A quaternary ammonium compound of the general formula CuHuCON-OHs-N(tel't)-Cl wherein N(tert) stands for the molecule of anitrogenoustertiary base, said compound being obtainable by reactingN-methyl-stearamido- I wherein N(tert) stands for the molecule of anithe group consisting of aliphatic and cycloaliphatic hydrocarbonradicals, while X stands for halogen.

2. A quaternary compound of the general formula wherein Y stands for analiphatic hydrocarbon radical having not less than 9 carbon atoms, Rstands for a member of the group consisting of aliphatic andcycloaliphatic hydrocarbon radicals of not more than 7 carbon atoms,1*;(tert) methyl-chloride with a tertiary nitrogenous base, and being asolid, soluble in water, alcohol, warm benzene and. ethylenedichloride.

6. A quaternary general formula trogenous tertiary base, said compoundbeing obtainable by reactingN.-carbomethoxy-heptadecylamino-methyl-chloride with a tertiaryniammonium compound of thetrogenous base, and being a solid, soluble in'water, alcohol, warm benzen and ethylenedichloride.

7. A process of preparing quaternary compounds of the general formula asdefined in claim 1, which comprises reacting a tertiary base with acompound of the general formula wherein Y stands for a radical of thegroupconsisting of alkyl, alkoxy, cycloalkyl and cycloalkoxy, R standsfor a member of th group consisting of aliphatic and cycloaliphatichydrocarbon radicals, while X stands for halogen.

8. A process of preparing quaternary compounds of the general formula asdefined in claim 2, which comprises reacting a tertiary base with acompound of the general formula whereimY stands for an aliphatichydrocarbon radical having not less than 9 carbon atoms, R stands for amember of the group consisting of aliphatic and cycloaliphatichydrocarbon radicals of not more than '7 carbon atoms, while X standsfor halogen.

9. A quaternary compound of the general formula n-o-c 0-N-CHr-N (mm-xwherein R and R are aliphatic hydrocarbon radicals of which R has atleast 4 carbon atoms, N(tert) stands for the molecule of a nitrogenous vtertiary base, while It stands for halogen.

10. N-cyclohexyl-lauramidomethyl-pyridinium chloride. L

11. N methyl stearamidomethyl pyridinium chloride.

12. N-carbomethoxy-heptadecylamino-methylpyridinlum chloride.

13. A process of preparing quaternary compounds of the general formulaas defined in claim 5 9, which comprises reacting a tertiary base with acompound 01 the general formula R-O-OO-N-CHr-X m wherein R and R arealiphatic hydrocarbonradicals of which R has at least 4 carbon atoms,while X stands for halogen.

ALFRED WILLIAM BALDWIN. HENRY ALFRED PIGGO'I'I.

